Rapid Solid-Phase Sulfurization Growth and Nonlinear Optical Characterization of Transfer-Free TiS₃ Nanoribbons

Abstract

Quasi-1D titanium trisulfide (TiS3) has strong in-plane anisotropy with a direct band gap of about 1 eV, which has attracted wide attention in the fields of microelectronics and optoelectronics. However, the investigation of in situ synthesis, synthetic mechanism, and nonlinear optical properties of TiS3 is rarely reported. In this work, we developed a transfer-free method to grow TiS3 nanoribbons, successfully reducing the synthesis time from a few days to less than 24 h without pretreatment. Raman spectroscopy revealed TiS3 was not directly synthesized by titanium (Ti) and sulfur (S) but by the further sulfurization reaction of intermediate product TiS2. Moreover, the polarized four-wave mixing (FWM) imaging of the as-grown TiS3 samples was conducted by ultrafast nonlinear optical spectroscopy for the first time, identifying the crystal axis orientation of TiS3 accurately and quickly. Our work not only provides a rapid growth method for transfer-free synthesis of TiS3 nanoribbons on SiO2/Si substrates but also investigate the fast and non-destructive ultrafast nonlinear optical characterization of quasi-1D TiS3, which lays a foundation for understanding the synthetic mechanism and physicochemical properties of transition metal trisulfides (TMTCs) and promoting the functional device applications of TMTCs represented by TiS3.

Comment on “Rapid Solid-Phase Sulfurization Growth and Nonlinear Optical Characterization of Transfer-Free TiS3 Nanoribbons”

“…Several prior studies focused on the photoemission spectroscopy characterization of TiS 3 contain rigorous discussions on the S 2p core level XPS spectra. − The expectation is that there is more electron donation between Ti and S 2– (sulfide) than between Ti and S 2 2– (disulfide). This phenomenon manifests itself in higher binding energy for the S 2 2– 2p core-level doublet than that of the S 2– 2p core-level doublet, − as opposed to what is reported in ref .…”

“…Zhang et al have done a commendable job of developing a highly time-efficient method for the synthesis of TiS 3 . While the experimental data presented in their work are of high quality, the current fits to their high-resolution X-ray photoemission spectroscopy (XPS) data for the S 2p core level (Figure 3b of ref ) are in line with neither prior work − nor expectations.…”

What happens when transition metal trichalcogenides are interfaced with gold?

“…While there exist several photoemission spectroscopy studies on these three TMTs (i.e., TiS 3 [36,52,68,69,74,89], ZrS 3 [52,69,89,90], and HfS 3 [73]), a comparison of the corelevel photoemission data for the sulfur core-levels of each of these trichalcogenides can provide indications of predominant location of the sulfur vacancies [98,99]. In the case of HfS 3 , such a comparison can help identify the location of sulfur sites that are filled in by oxygen instead.…”

“…Their quasi-1D structure helps combat detrimental edge scattering and unfavorable edge states, which have detrimental effects on the performance of nanodevices as the transistor channel widths shrink to 10 nm or less [18,[27][28][29][30][31][32]. This makes the TMTs attractive for a plethora of low-dimensional device applications [33][34][35][36][37][38][39][40][41][42][43][44][45][46]. Owing to their low-symmetry [47][48][49][50][51], the TMTs are also great for highly anisotropic optoelectronic applications [43][44][45][52][53][54][55][56].…”

Reply to Comment on “Rapid Solid-Phase Sulfurization Growth and Nonlinear Optical Characterization of Transfer-Free TiS3 Nanoribbons”

“…Second, Dr. Dhingra mentioned that the binding energy of the S 2 2− 2p core-level doublet is higher than the S 2− 2p core-level doublet, which is opposed to our previous description. 2 Third, Dr. Dhingra mentioned that correct data fitting can indicate whether it is the S 2− sulfur vacancies or the S 2 2− sulfur vacancies that render TiS 3 n-type.…”